JP2023153541A - Production method of polyolefin modified body - Google Patents

Abstract

To provide a production method for producing a polyolefin modified body, capable of introducing an isocyanate group to a polyolefin, in a short step and in an industrially advantageous condition.SOLUTION: There is provided a production method for producing a polyolefin modified body including, a step for addition reaction of a polyolefin whose carbon-carbon double bond terminal ratio is 20% or greater, and a compound expressed by a general formula I: the polyolefin modified body has at least one isoxazoline skeleton and at least one isocyanate group; in any order, the double bond of the polyolefin and at least one nitrile oxide group of the compound is subjected to addition reaction; and at least one nitrile oxide group in the compound is converted into the isocyanate group.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for producing a modified polyolefin.

Polyolefins such as polyethylene and polypropylene have excellent moldability and mechanical properties, so they are used in a wide range of fields such as industrial applications and household material applications as films, sheets, fibers, nonwoven fabrics, molded products (containers, etc.), modifiers, etc. has been done.

Since polyolefin has a saturated hydrocarbon skeleton, it is known that it has poor reactivity and is difficult to modify the resin. It is also known that it has poor compatibility with different resins. As a method for solving these problems, a method of modifying polyolefin with peroxide is known. However, in this method, a crosslinking reaction proceeds in polyethylene, and a decrease in molecular weight due to molecular chain scission occurs in polypropylene as a side reaction.

In recent years, attempts have been made to introduce polar functional groups into polyolefins having a carbon-carbon double bond at one of the two ends of the main chain (Patent Document 1). If a polar functional group can be introduced into the terminal carbon-carbon double bond through a chemical reaction, reactive points can be introduced into the polyolefin, thereby improving reactivity. That is, by reacting the introduced polar functional group with a different resin, it becomes possible to produce a block copolymer, which enables adhesion and compatibilization with other polymers.

It is known that compounds having isocyanate groups are widely used as crosslinking agents and modifiers in metal, wood, automobile refinishing paints, etc. (Patent Documents 2 and 3). Compounds having an isocyanate group are useful as reactants in various uses because they easily undergo addition reactions with active hydrogen compounds such as amine groups and hydroxyl groups due to the resonance structure of the isocyanate group.

International Publication No. 2019/107450 JP2020-62821A JP 2021-75717 Publication

Methods for introducing isocyanate groups into polyolefins include the use of peroxides and reaction in a solvent, but these methods are industrially disadvantageous as they require multiple steps and a large amount of solvent. It was technology.

An object of the present invention is to provide a method for producing a modified polyolefin, which can introduce isocyanate groups into a polyolefin in a short process and under industrially advantageous conditions.

The present inventors conducted multifaceted considerations and experimental searches to solve the above problems, and found that by using a polyolefin having a specific structure and a specific compound having a nitrile oxide group, a short process and an industrial solution can be achieved. The present inventors have discovered that isocyanate groups can be introduced into polyolefins under economically advantageous conditions, and have completed the present invention.
The present invention relates to the following [1] to [7].

[1] A method for producing a modified polyolefin, which comprises subjecting a polyolefin having a carbon-carbon double bond terminal ratio of 20% or more to an addition reaction with a compound represented by the following general formula [I], The modified polyolefin has at least one isoxazoline skeleton and at least one isocyanate group,
A manufacturing method comprising, in any order, adding-reacting the double bond of the polyolefin with at least one nitrile oxide group of the compound, and converting at least one of the nitrile oxide groups in the compound into an isocyanate group. .

In the general formula [I], s is an integer of 2 to 4; R ¹ and R ² are each independently a hydrocarbon group having 4 to 10 carbon atoms or a halogenated hydrocarbon group having 4 to 10 carbon atoms. is a hydrogen group; each X is independently a divalent hydrocarbon group, -O-, -S-, or -N(R ³ )-; R ³ is a hydrogen atom or a carbon atom having 1 to 6 carbon atoms; is a hydrocarbon group; A is an s-valent organic group.
[2] A method for producing a modified polyolefin, the method comprising carrying out an addition reaction between a polyolefin having a carbon-carbon double bond terminal ratio of 20% or more and a compound represented by the following general formula [I], The polyolefin modified product is represented by the following general formula [II],
A manufacturing method comprising, in any order, adding-reacting the double bond of the polyolefin with at least one nitrile oxide group of the compound, and converting at least one of the nitrile oxide groups in the compound into an isocyanate group. .


In the general formulas [I] and [II], s is an integer of 2 to 4; n is an integer of 1 to 3; s>n; R ¹ and R ² are each independently is a hydrocarbon group having 4 to 10 carbon atoms or a halogenated hydrocarbon group having 4 to 10 carbon atoms; X is each independently a divalent hydrocarbon group, -O-, -S- or - N(R ³ )-; R ³ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; A is an s-valent organic group; R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; R ⁷ is the main chain of the polyolefin.
[3] The method for producing a modified polyolefin according to [1] or [2], wherein the step of converting at least one nitrile oxide group in the compound into an isocyanate group is performed in the presence of an isomerization promoter.
[4] The method for producing a modified polyolefin according to any one of [1] to [3], wherein the polyolefin and the compound are subjected to an addition reaction under conditions substantially free of a solvent.
[5] The step of causing an addition reaction between the double bond of the polyolefin and at least one nitrile oxide group of the compound, and the step of converting at least one of the nitrile oxide groups in the compound into an isocyanate group, The method for producing a modified polyolefin according to any one of [1] to [4], which is carried out in one operation of melt-kneading a mixture of compounds at 80 to 300°C.
[6] The method for producing a modified polyolefin according to any one of [1] to [5], wherein the carbon-carbon double bond of the polyolefin is a vinyl group or a vinylidene group.
[7] A modified polyolefin obtained by the production method described in any one of [1] to [6].

According to the method for producing a modified polyolefin of the present invention, isocyanate groups can be introduced into a polyolefin in a short process and under industrially advantageous conditions.

FIG. 1 is a ¹ H-NMR spectrum of the modified polyolefin of Example 4.

The following definitions of terms apply throughout the specification and claims.
"Polyethylene" is an ethylene homopolymer or an ethylene-(α-olefin having 3 or more carbon atoms) copolymer in which the proportion of ethylene units exceeds 50 mol%. Polyethylene may have 1 mol% or less of diene compound units.
"Polypropylene" is a propylene homopolymer or propylene (ethylene or α-olefin having 4 or more carbon atoms) copolymer in which the proportion of propylene units is 50 mol% or more. Polypropylene may have 1 mol% or less of diene compound units.
"1,3-dipolar functional group" means a 1,3-dipolar cycloaddition reaction with an unsaturated bond (carbon-carbon double bond, carbon-carbon triple bond, carbon-nitrogen triple bond, etc.). refers to the functional group obtained.
"Main chain" refers to a linear molecular chain in which all molecular chains other than the main chain are considered pendant.
"Substantially no solvent" means that there is no solvent other than the solvent unavoidably mixed during production.
"~" indicating a numerical range means that the numerical values written before and after it are included as lower and upper limits.

<Method for producing modified polyolefin>
The method for producing a modified polyolefin includes a polyolefin having a carbon-carbon double bond terminal ratio of 20% or more (hereinafter also referred to as "double bond-containing polyolefin") and a compound represented by the following general formula [I]. The modified polyolefin has at least one isoxazoline skeleton and at least one isocyanate group, and the production method includes adding a double bond of the polyolefin and a nitrile oxide group of the compound in any order. and a step of converting at least one nitrile oxide group in the compound into an isocyanate group.

In the general formula [I], s is an integer of 2 to 4; R ¹ and R ² are each independently a hydrocarbon group having 4 to 10 carbon atoms or a halogenated hydrocarbon group having 4 to 10 carbon atoms. is a hydrogen group; each X is independently a divalent hydrocarbon group, -O-, -S-, or -N(R ³ )-; R ³ is a hydrogen atom or a carbon atom having 1 to 6 carbon atoms; is a hydrocarbon group; A is an s-valent organic group.

[Double bond-containing polyolefin]
Examples of the "polyolefin" in the double bond-containing polyolefin include polyethylene, polypropylene, and the like. One type of double bond-containing polyolefin may be used alone, or two or more types may be used in combination.
Polyethylene may have more than 0 mol% and less than 50 mol% of α-olefin other than ethylene as a comonomer. Further, it may contain more than 0 mol% and 1 mol% or less of a diene compound as a comonomer. The content of diene as a comonomer is preferably 0 mol%.
Polypropylene may have more than 0 mol% and 50 mol% or less of α-olefin other than propylene as a comonomer. Further, it may contain more than 0 mol% and 1 mol% or less of a diene compound as a comonomer. The content of diene as a comonomer is preferably 0 mol%.
Examples of the α-olefin include ethylene, propylene, butene, hexene, octene, and 4-methyl-1-pentene.
Examples of the diene compound include vinylnorbornene, dicyclopentadiene, ethylidene norbornene, and 1,4-hexadiene.

From the viewpoint of reactivity, the carbon-carbon double bond terminal ratio in the double bond-containing polyolefin is 20% or more, preferably 40% or more, and more preferably 60 to 200%. The double bond-containing polyolefin may have a carbon-carbon double bond in the middle of the main chain, and may have a carbon-carbon double bond at the end or in the middle of the side chain.
Here, the carbon-carbon double bond terminal ratio means the abundance ratio of terminal carbon-carbon double bond groups per molecular chain of the double bond-containing polyolefin. When all of the double bond-containing polyolefins have a carbon-carbon double bond group at only one end, the carbon-carbon double bond terminal ratio is 100%. The carbon-carbon double bond termination ratio can take a value of 0 to 200%. Note that the carbon-carbon double bond at the end of the side chain is not included in the calculation of the carbon-carbon double bond terminal ratio in the double-bond-containing polyolefin.

As the carbon-carbon double bond, a vinyl group and a vinylidene group are preferred. As the carbon-carbon double bond, a vinyl group is preferable since it has excellent reactivity with the nitrile oxide group of the compound represented by the general formula [I]. The nitrile oxide group, which is a 1,3-dipole functional group, is more reactive towards sterically small olefin bonds than towards sterically large olefin bonds.

When the double bond-containing polyolefin is double bond-containing polypropylene, the polypropylene generally has the following terminal groups. Examples of structures in which the terminal end is a vinyl group include structural formulas (1-a) and (1-f). A structure in which the terminal end is a vinylidene group includes structural formula (1-b).

Furthermore, when the double bond-containing polyolefin is double bond-containing polypropylene, due to the reaction mechanism, in addition to regular monomer units inside the polymer chain, the following internal olefins are generated to form the polymer. It may become a monomer unit.

Double bond-containing polyolefins can generally be produced by coordination polymerization of α-olefins using a transition metal catalyst and without using a chain transfer agent. Usually, during the production of polyolefins, the molecular weight is controlled using a chain transfer agent, so the terminal structure of polyolefins is saturated terminals. On the other hand, in coordination polymerization using a transition metal catalyst, when a chain transfer agent such as hydrogen or organoaluminum is not used, the terminal end of the polyolefin becomes a carbon-carbon double bond. Particularly, terminal double bonds are likely to be formed in a polymerization system in which the molecular weight is controlled by the polymerization temperature. Furthermore, along with hydrogen generation, carbon-carbon double bonds may be formed in the middle of the main chain and in side chains. Regarding these, see Macromolecules, Volume 38, 2005, p. 6988-6996 and Topics in Catalysis, Volume 7, 1999, p. 145-163 etc.

Examples of transition metal catalysts include complex catalyst systems (Phillips catalysts, metallocene catalysts, post-metallocene catalysts, etc.), Ziegler-Natta catalyst systems, etc. Phillips catalysts, metallocene catalysts, and post-metallocene catalysts are preferred and are said to have a wide range of production possibilities. From this point of view, metallocene catalysts and post-metallocene catalysts are particularly preferred. In addition, a chain transfer agent may be added to the system if necessary in a small amount.

(Calculation method of carbon-carbon double bond terminal ratio)
The carbon-carbon double bond terminal ratio means the proportion of molecular chains having a carbon-carbon double bond group at the terminal among all polymer chains of the double bond-containing polyolefin. Calculation of the carbon-carbon double bond terminal ratio can be performed according to the method described in JP-A-2021-4376.

Specifically, the carbon-carbon double bond terminal ratio is calculated by the following formula.
(Carbon-carbon double bond terminal ratio) = (total number of carbon-carbon double bond terminals) / {((total number of terminals) - (number of LCB)) ÷ 2} x 100
Here, the total number of carbon-carbon double bond ends is the total number of carbon-carbon double bond ends per 1000 monomer units calculated by ¹ H-NMR. The total number of terminals is the total number of terminals per 1000 monomer units calculated by ¹ H-NMR and ¹³ C-NMR. The LCB number is the number of methine carbons at the root of a branched chain having 7 or more carbon atoms per 1000 monomer units calculated by ¹³ C-NMR.

Below, a method for specifying the terminal ratio of carbon-carbon double bonds using ¹ H-NMR and ¹³ C-NMR for double bond-containing polypropylene will be explained.

1. Sample preparation and measurement conditions 200 mg of sample was placed in an NMR sample tube with an inner diameter of 10 mm along with 2.4 ml of o-dichlorobenzene/deuterated bromide benzene (C ₆ D ₅ Br) mixed solution and hexamethyldisiloxane, which is a reference material for chemical shift. and uniformly melt using a block heater at 150°C.
The NMR measurement is performed at 120° C. using an AV400 NMR apparatus manufactured by Bruker Biospin Inc. equipped with a 10 mmφ cryoprobe.
¹ H-NMR is used to quantify the number of terminal carbon-carbon double bonds. The measurement conditions for ¹ H-NMR are a sample temperature of 120° C., a pulse angle of 4.5°, a pulse interval of 2 seconds, and a total number of 512 times. For chemical shifts, the proton signal of hexamethyldisiloxane is set at 0.09 ppm, and chemical shifts of signals due to other protons are based on this.
¹³ C-NMR is used to quantify saturated ends. The measurement conditions for ¹³ C-NMR are that the sample temperature is 120° C., the pulse angle is 45°, the pulse interval is 18 seconds, the number of integrations is 3072, and the measurement is performed using a broadband decoupling method. For the chemical shift, the ¹³ C signal of hexamethyldisiloxane is set at 1.98 ppm, and the chemical shifts of other ¹³ C signals are based on this.

2. Method for calculating the number of terminal carbon-carbon double bonds Examples of structures in which the terminal is a vinyl group include the above-mentioned structural formulas (1-a) and (1-f). In ¹ H-NMR, the proton signals of the unsaturated bonds of structural formula (1-a) 1-propenyl and structural formula (1-f) 1-butenyl are 5.08 to 4.85 ppm in the ¹ H-NMR spectrum. and 5.86 to 5.69 ppm signals are detected. Therefore, the number of terminal vinyl groups [Vi] is calculated as the total number of 1-propenyl and 1-butenyl, as the amount of unsaturated bonds per 1000 monomers in total, and using the signal intensity of the ¹ H-NMR spectrum, using the following formula: Find from.
Structural formula (1-a) + Structural formula (1-f): [Vi] = Ivi×1000/Itotal

Examples of structures in which the terminal end is a vinylidene group include the above-mentioned structural formula (1-b). The number of terminal vinylidene groups [Vd] is determined as the number of propyl-vinylidene, as the amount of unsaturated bonds per 1000 monomers in total, and using the signal intensity of ^{the 1} H-NMR spectrum from the following formula.
Structural formula (1-b): [Vd]=Ivd×1000/Itotal
Similarly, the number of i-butenyl groups [i-butenyl], the number of vinylene terminals [terminal vinylene], and the number of internal vinylidenes [internal vinylidene] are determined from the following formulas.
Structural formula (1-d): [i-butenyl]=Iibu×1000/Itotal
Structural formula (1-g): [terminal vinylene]=Ivnl×1000/Itotal
Structural formula (1-m): [internal vinylidene]=Iivd×1000/Itotal

Here, Ivi, Ivd, Iibu, Ivnl and Iivd are, respectively, structural formula (1-a) + structural formula (1-f), structural formula (1-b), structural formula (1-d), and structural formula (1-g) and the characteristic value of the signal based on the structural formula (1-m), and is the amount shown by the following formula.
Ivi=(I _5.08~4.85 +I _5.86~5.69 )/3,
Ivd=(I _4.79~4.65 )/2,
Iibu=I _5.30~5.08 ,
Ivnl=(I _5.58~5.30 )/2,
Iivd=(I _4.85~4.79 )/2

I indicates the integrated intensity, and the subscript number of I indicates the range of chemical shift. For example, I _5.08-4.85 indicates the integrated intensity of the signal detected between 5.08 ppm and 4.85 ppm.
Moreover, Itotal is a quantity shown by the following formula.
Itotal=IC3+Ivi+Ivd+Iibu+Ivnl+Iivd
IC3 represents a characteristic value of a signal based on propylene, and is an amount expressed by the following formula.
IC3=1/6×Imain
Imain is the sum of the proton signals of the polymer main chain and the saturated end detected at 4.00 to 0.00 pm in the ¹ H-NMR spectrum.

3. Method for calculating the number of saturated ends The number of saturated ends described below is determined as the number per 1000 monomers using the signal intensity of the ¹³ C-NMR spectrum from the following formula.
Structural formula (1-c): [i-butyl]=Ii-butyl×1000/Itotal-C
Structural formula (1-e): [n-butyl]=Inbu×1000/Itotal-C
Structural formula (1-h): [n-propyl]=Inpr×1000/Itotal-C
Structural formula (1-i): [2,3-dimethylbutyl]=I2,3-dime×1000/Itotal-C
Structural formula (1-j): [3,4-dimethylpentyl]=I3,4-dime×1000/Itotal-C

Furthermore, the propylene homopolymer of the present disclosure has, in addition to the structure based on regular 1,2 insertion of propylene inside the polymer, the following 2,1 bonds and 1,3 bonds based on irregular insertion of propylene. Can have bonds.

Here, Ii-butyl, Inbu, Inpr, I2,3-dime, and I3,4-dime are structural formula (1-c), structural formula (1-e), structural formula (1-h), and structural formula (1-h), respectively. It represents a characteristic value of a signal based on formula (1-i) and structural formula (1-j), and is a quantity shown by the following formula.
Ii-butyl=(I _23.80~23.70 +I _25.80~25.70 )/2
Inbu=I _14.06~14.02
Inpr=(I _14.44~14.42 +I _30.46~30.45 )/2
I2,3-dime=(I _16.21~16.17 +I _31.86~31.81 )/2
I3,4-dime=I _12.0-11.60

Furthermore, Itotal-C is an amount expressed by the following formula.
Itotal-C=Ii-butyl+Inbu+Inpr+I2,3-dime+I3,4-dime+I1,2-P+I2,1-P+I1,3-P
I1,2-P is the characteristic value of the signal based on the bond of propylene inserted with 1,2, I2,1-P is the characteristic value of the signal based on the bond of propylene inserted with 2,1, and I1,3-P is the characteristic value of the signal based on the bond of propylene inserted with 2,1. , represents the characteristic value of the signal based on the bond of propylene inserted with 1,3, and is the amount shown by the following formula.
I1,2-P=I _48.80-44.50
I2,1-P=(I _35.72~35.63 +I _35.83~35.77 )/2
I1,3-P=I _37.41-37.21 /2

4. Calculation method for total number of terminals The total number of terminals is the total number of terminals per 1000 monomer units calculated by each of ¹³ C-NMR and ¹ H-NMR, and specifically, the number of terminals per 1000 monomer units. This is the total number of terminals from (1-a) to structural formula (1-j).

5. Method for calculating LCB number Double bond-containing polypropylene may have a long chain branch (LCB) structural part.
The number of long chain branches (LCB number) is 31.72 to 31.66 ppm branching when the intensity of methylene carbon in the propylene main chain of 49.00 to 44.33 ppm is normalized to 1000 by ¹³ C-NMR. Signal integration of three methylene carbons bonded to point carbon (methine carbon) and branch point carbons (methine carbon) at 44.09 to 44.03 ppm, 44.78 to 44.72 ppm, and 44.90 to 44.84 ppm It is calculated by the following formula using the intensity, and the number is calculated per 1000 propylene monomer units.
LCB number = [(I _44.09~44.03 +I _44.78~44.72 +I _44.90~44.84 +I _31.72~31.66 )/4]/I _49.00~44.33

[Compound represented by general formula [I]]
The compound represented by the general formula [I] has a nitrile oxide group which is a 1,3-dipole functional group. The nitrile oxide group can undergo a 1,3-dipolar cycloaddition reaction with the unsaturated bonds of the double bond-containing polyolefin in the absence of a catalyst to form an isoxazoline skeleton. Further, the compound represented by the general formula [I] is advantageous in that the nitrile oxide group is difficult to dimerize and allows the 1,3-dipolar cycloaddition reaction to proceed. The compounds represented by the general formula [I] may be used alone or in combination of two or more.

In general formula [I], s is an integer of 2 to 4. From the viewpoint of suppressing the reaction between polymers, s is preferably an integer of 2 to 3, and more preferably 2.

R ¹ and R ² are each independently a hydrocarbon group having 4 to 10 carbon atoms or a halogenated hydrocarbon group having 4 to 10 carbon atoms. Examples of the hydrocarbon group having 4 to 10 carbon atoms or the halogenated hydrocarbon group having 4 to 10 carbon atoms include tert-butyl group, isobutyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methyl Examples include phenyl group, 4-chlorophenyl group, 2,4-dimethylphenyl group, and 3,4-dimethylphenyl group.
R ¹ and R ² are preferably aryl groups having 6 to 8 carbon atoms, since the nitrile oxide group is difficult to dimerize. Examples of the aryl group having 6 to 8 carbon atoms include phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,4-dimethylphenyl group, 4-chlorophenyl group, etc. A 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2,4-dimethylphenyl group are preferable, and a phenyl group is more preferable.
R ¹ and R ² may be the same or different. R ¹ and R ² are preferably the same because the symmetry of the molecule is increased, the compound is easily solidified, and the storage stability at room temperature is excellent.

Each X is independently a divalent hydrocarbon group, -O-, -S-, or -N(R ³ )-. From the viewpoint of easy synthesis of the compound, X is preferably -O-, -S- or -N(R ³ )-, preferably -O- or -S-, and more preferably -O-.
R ³ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Examples of the hydrocarbon group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, and hexyl group. R ³ is preferably a hydrogen atom or a methyl group from the viewpoint of easy synthesis of the compound.
Examples of the divalent hydrocarbon group for X include alkylene groups having 1 to 3 carbon atoms, arylene groups having 6 to 8 carbon atoms, and combinations thereof.

A is an s-valent organic group. The organic group essentially contains a carbon atom, and optionally contains a hydrogen atom, an oxygen atom, a chlorine atom, a nitrogen atom, a sulfur atom, or the like. Examples of organic groups include hydrocarbon groups (alkylene groups, arylene groups, etc.), hydrocarbon groups and various bonds (-O-, -C(=O)-, -S-, -S(=O) ₂ -, etc.) combinations, combinations of hydrocarbon groups and polar functional groups (hydroxy group, mercapto group, carboxy group, amino group, amide group, alkoxy group, etc.), combinations of hydrocarbon groups and various bonds and polar functional groups, etc. Can be mentioned.

As the compound represented by the general formula [I], the following nitrile oxide compounds (i) to (ii) are preferable because they tend to have a high melting point and have excellent storage stability at room temperature.
(i) A nitrile oxide compound in the general formula [I], where s is 2 and A is an alkylene group having 2 to 10 carbon atoms.
(ii) A nitrile oxide compound in which s is 2 in general formula [I] and A is a group represented by general formula [III] described below.

By introducing an alkylene group with high symmetry and a short carbon chain as in (i), the melting point of the nitrile oxide compound can be increased.
By introducing a group represented by general formula [III] having a highly symmetrical and rigid arylene group like (ii), the melting point of the nitrile oxide compound can be increased.

A in (i) is an alkylene group having 2 to 10 carbon atoms. A in (i) is preferably an alkylene group having 3 to 8 carbon atoms, more preferably an alkylene group having 4 to 6 carbon atoms, from the viewpoint of solidifying the nitrile oxide compound and developing a melting point close to that of polyolefin.
A in (i) is a 1,2-ethylene group, a 1,3-propylene group, a 2-methyl-1,3-propylene group, a 2,2-dimethyl-1,3-propylene group, a 1,4- Butylene group, 1,5-pentylene group, 1,6-hexylene group, 1,7-heptylene group, 1,8-octylene group, 3-methyl-1,5-pentylene group, 1,4-cyclohexylene group , 1,4-cyclohexadimethylene group, 1-methyl-1,2-ethylene group, 1-methyl-1,3-propylene group, and the like. A in (i) is a 1,3-propylene group, a 1,4-butylene group, a 1,6-hexylene group, a 1,4-cyclohexadimethylene group, a 1,4-cyclohexylene group, a 3-methyl -1,5-pentylene group is preferred, and 1,4-butylene group, 1,6-hexylene group, and 3-methyl-1,5-pentylene group are more preferred.

A in (ii) is a group represented by general formula [III].
-(R ⁴ ′-O) _t -R ⁵ ′-(O-R ⁴ ′) _t - ... [III]

t is 0 or 1. t is preferably 1 from the viewpoint of ease of production of the nitrile oxide compound, and preferably 0 from the viewpoint of the melting point of the nitrile oxide compound.
R ^4' is an alkylene group having 2 to 4 carbon atoms. Examples of R ^4' include 1,2-ethylene group and 1,3-propylene group. As R ^4' , a 1,2-ethylene group is preferable since the smaller the number of carbon atoms, the higher the melting point of the nitrile oxide compound.

R ^5' is a group represented by the general formula [IV] or a group represented by the general formula [V]. R ^5' is preferably a group represented by the general formula [V] from the viewpoint of increasing the distance between the terminal end of the polyolefin and the introduced functional group after modification of the double bond-containing polyolefin and increasing the reactivity of the modified polyolefin. .

R ^6' to R ^9' are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ^6' and R ^7' are linked to form an aromatic ring or an aliphatic ring. or R ^8' and R ^9' may be connected to form an aromatic ring or an aliphatic ring. Examples of the hydrocarbon group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, and phenyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R ^6' to R ^9' are preferably a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a phenyl group, or a chlorine atom, and more preferably a hydrogen atom, a methyl group, an isopropyl group, or a tert-butyl group. Preferably, a hydrogen atom and a methyl group are more preferable.

R ^10' to R ^17' are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ^10' and R ^11' are linked to form an aromatic ring or an aliphatic ring. R ^12' and R ^13' may be connected to form an aromatic ring or an aliphatic ring, and R ^14' and R ^15' may be connected to form an aromatic ring or an aliphatic ring. or R ^16' and R ^17' may be connected to form an aromatic ring or an aliphatic ring. Examples of the hydrocarbon group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, and phenyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R ^10' to R ^17' are preferably a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a phenyl group, or a chlorine atom, and more preferably a hydrogen atom, a methyl group, an isopropyl group, or a tert-butyl group. Preferably, a hydrogen atom and a methyl group are more preferable.

u is 0 or 1. u is preferably 1 from the viewpoint of increasing the distance between the terminal end of the polyolefin and the introduced functional group after modification of the double bond-containing polyolefin and increasing the reactivity of the modified polyolefin.
Q is -C(R ^18' )(R ^19' )-, -C(=O)-, -S- or -S(=O) ₂ -. Q is more preferably -C(R ^18' )(R ^19' )- from the standpoint of increasing solubility in polyolefin during melt-kneading.
R ^18' and R ^19' are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ^18' and R ^19' are linked to form an aromatic ring or an aliphatic ring. may be formed. Examples of the hydrocarbon group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, and phenyl group. An example in which R ^18' and R ^19' are linked is a 1,1-cyclohexylene group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. As R ^18' and R ^19' , a hydrogen atom, a methyl group, an ethyl group, and a phenyl group are preferable.

The melting point of the compound represented by formula [I] is preferably 25 to 300°C, more preferably 40 to 280°C, even more preferably 60 to 260°C, and particularly preferably 80 to 240°C. If the melting point of the compound is equal to or higher than the lower limit of the above range, the mobility at room temperature will be reduced, and therefore the storage stability at room temperature will be improved. If the melting point of the compound is below the upper limit of the range, the compound will easily melt during the melting reaction and the reactivity will increase.
In order to make the melting point of the compound represented by the general formula [I] 25°C or higher, for example, a highly symmetrical structure is added to A to increase the symmetry of the molecular structure, or a highly rigid group is added to A. or introduce short-chain groups.

[Method for producing modified polyolefin]
The method for producing a modified polyolefin includes addition-reacting a polyolefin having a terminal carbon-carbon double bond ratio of 20% or more with a compound represented by the general formula [I]. The production method includes, in any order, addition-reacting the double bond of the polyolefin with at least one nitrile oxide group of the compound represented by general formula [I]; The step of converting one into an isocyanate group is included. By the production method of the present invention, a modified polyolefin having at least one isoxazoline skeleton and at least one isocyanate group can be produced in a short process and under industrially advantageous conditions.

The compounding amount of the compound represented by general formula [I] is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 8 parts by weight, and 0.001 to 10 parts by weight, more preferably 0.01 to 8 parts by weight, per 100 parts by weight of the double bond-containing polyolefin. More preferably 05 to 6 parts by mass. Furthermore, the compounding amount of the compound represented by general formula [I] shall be 0.1 to 8.0 equivalents per equivalent of carbon-carbon double bonds in the double bond-containing polyolefin. is preferable, the amount is more preferably 0.5 to 5.0 equivalents, and even more preferably the amount is 1.0 to 3.0 equivalents.

(isomerization accelerator)
The step of converting at least one nitrile oxide group in the compound represented by general formula [I] into an isocyanate group is preferably carried out in the presence of an isomerization promoter.
The isomerization promoter is a component that promotes the reaction of converting the nitrile oxide group of the compound into an isocyanate group. By carrying out an addition reaction between a double bond-containing polyolefin and the above-mentioned compound in the presence of an isomerization promoter, it is easy to efficiently produce a modified polyolefin having at least one isoxazoline skeleton and at least one isocyanate group in a short process. Become.

Examples of the isomerization accelerator include fatty acid compounds such as stearic acid and lauric acid, fatty acid amide compounds such as stearic acid amide and oleic acid amide, and fatty acid metal salt compounds such as calcium stearate, calcium laurate, and zinc octylate. . From the viewpoint of isomerization promotion efficiency, those having stearic acid as the main skeleton are more preferable, and calcium stearate is even more preferable. The isomerization promoters may be used alone or in combination of two or more.

The blending amount of the isomerization accelerator is preferably 0.001 to 10 parts by weight, more preferably 0.005 to 8 parts by weight, and 0.01 to 6 parts by weight based on 100 parts by weight of the double bond-containing polyolefin. More preferred. The amount of the isomerization accelerator is preferably 0.005 to 1 equivalent, and preferably 0.01 to 0. The amount is more preferably .8 equivalent, and even more preferably 0.05 to 0.4 equivalent.

The polyolefin modified product is obtained, for example, by mixing a double bond-containing polyolefin and a compound represented by the general formula [I] in the presence or absence of an isomerization promoter and heat-treating the mixture. The heat treatment may be performed in a solvent, or may be performed while melt-kneading under conditions substantially free of solvent.

Examples of the solvent include hydrocarbons (toluene, xylene, hexane, cyclohexane, etc.). When a solvent is used, the mixing temperature is preferably 50 to 200°C, more preferably 60 to 180°C, even more preferably 80 to 150°C. When a solvent is used, the mixing time is preferably 30 minutes to 24 hours, more preferably 1 to 15 hours, and even more preferably 2 to 10 hours.

From the viewpoint of productivity, the heat treatment is preferably performed by melt-kneading under conditions substantially free of solvent to cause an addition reaction between the double bond-containing polyolefin and the compound represented by the general formula [I].

Examples of the melt-kneading method include methods using known devices such as a twin-screw extruder and a Banbury mixer. Details of the melt-kneading method can be found, for example, in "Thermoplastic Elastomers 2nd. ed.", Hanser Gardner Publications, 1996, p. 153-190.
When performing melt-kneading, all the components may be melt-kneaded at once, or some components may be melt-kneaded and then the remaining components may be added and melt-kneaded. Melt-kneading may be performed two or more times. Additional heat treatment may be performed after melt-kneading.

When substantially no solvent is present, that is, when melt-kneading is performed, the melt-kneading temperature is preferably 80 to 300°C. By melt-kneading a mixture of a double bond-containing polyolefin and a compound represented by general formula [I] at 80 to 300°C, an addition reaction between the double bond of the polyolefin and at least one nitrile oxide group of the compound is performed. The step of converting and the step of converting at least one of the nitrile oxide groups in the compound into an isocyanate group can be performed in one operation, which is advantageous in terms of productivity.
The melt-kneading temperature is more preferably 100 to 280°C, even more preferably 120 to 260°C. The kneading time refers to the residence time in melt kneading using an extruder. The melt-kneading time is preferably 1 second to 30 minutes, more preferably 10 seconds to 5 minutes.

(Mechanism of action)
In the method for producing a modified polyolefin of the present invention described above, since a polyolefin having a carbon-carbon double bond is used, the polyolefin is converted into the general formula (I) under industrially advantageous high temperature conditions. Can be modified with the compounds represented.

<Modified polyolefin>
The polyolefin modified product is obtained by a method for producing a polyolefin modified product. The modified polyolefin has at least one isoxazoline skeleton and at least one isocyanate group.

ｓは、２～４の整数であり、
ｎは、１～３の整数であり、
ｓ＞ｎであり、
Ｒ^１およびＲ^２は、それぞれ独立して、炭素数４～１０の炭化水素基または炭素数４～１０のハロゲン化炭化水素基であり、
Ｘは、それぞれ独立して、２価の炭化水素基、－Ｏ－、－Ｓ－または－Ｎ（Ｒ^３）－であり、
Ｒ^３は、水素原子または炭素数１～６の炭化水素基であり、
Ａは、ｓ価の有機基であり、
Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立して、水素原子または炭素数１～８のアルキル基であり、
Ｒ^７は、ポリオレフィンの主鎖である。 In another aspect of the present invention, the modified polyolefin is represented by the following general formula [II].

s is an integer from 2 to 4,
n is an integer from 1 to 3,
s>n,
R ¹ and R ² are each independently a hydrocarbon group having 4 to 10 carbon atoms or a halogenated hydrocarbon group having 4 to 10 carbon atoms,
X is each independently a divalent hydrocarbon group, -O-, -S- or -N(R ³ )-,
R ³ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms,
A is an s-valent organic group,
R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
R ⁷ is the main chain of the polyolefin.

In general formula [II], s is an integer of 2 to 4. From the viewpoint of suppressing the increase in viscosity of the modified polyolefin, s is preferably an integer of 2 to 3, and more preferably 2.

n is an integer from 1 to 3. From the viewpoint of using the polyolefin modified product as a filler dispersant and producing a block copolymer by reaction with other resins, n is preferably an integer of 1 to 2, and 1 is particularly preferred. However, s>n.

R ¹ and R ² are each independently a hydrocarbon group having 4 to 10 carbon atoms or a halogenated hydrocarbon group having 4 to 10 carbon atoms. Examples of R ¹ and R ² include those similar to R ¹ and R ² in general formula [I], and preferred embodiments are also the same.

X is each independently a divalent hydrocarbon group, -O-, -S-, or -N(R ³ )-, and R ³ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. be. A is an s-valent organic group. Examples of X, R ³ and A include those similar to X, R ³ and A in general formula [I], and preferred embodiments are also the same.

R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, isopropyl group, n-propyl group, n-butyl group, n-hexyl group, and the like. R ⁴ is preferably a hydrogen atom, methyl group, ethyl group, n-butyl group or n-hexyl group. As R ⁵ and R ⁶ , a hydrogen atom and a methyl group are preferable, and a hydrogen atom is more preferable, from the viewpoint of reducing steric hindrance around the double bond and increasing reactivity.

R ⁷ is the main chain of the polyolefin. Examples of the polyolefin include those similar to the "polyolefin" in the double bond-containing polyolefin, and preferred embodiments are also the same.

(Structure identification of modified polyolefin)
The isoxazoline skeleton of the modified polyolefin can be identified by ¹ H-NMR. Specifically, the modified polyolefin was placed in an NMR sample tube with an inner diameter of 10 mm along with an o-dichlorobenzene/deuterated bromide benzene (C ₆ D ₅ Br) mixed solution and hexamethyldisiloxane, which is a reference substance for chemical shift. , uniformly melt using a block heater at 150°C. The NMR measurement is performed at 120° C. using an AV400 NMR apparatus manufactured by Bruker Biospin Inc. equipped with a 10 mmφ cryoprobe.

FIG. 1 is a ¹ H-NMR spectrum of the modified polyolefin of Example 4. In the polyolefin modified product of Example 4, R ⁴ , R ⁵ and R ⁶ in general formula [II] are all hydrogen, but as shown in FIG. 1, the signal of the hydrogen atom of R ⁴ is 4.1 to 4. The signals of the hydrogen atoms of R ⁵ and R ⁶ were observed in the range of 2.3 to 3.0 ppm, and based on this, the isoxazoline skeleton can be identified. Similarly, when R ⁴ , R ⁵ and R ⁶ are alkyl groups having 1 to 8 carbon atoms, the isoxazoline skeleton can be identified by ¹ H-NMR.

Isocyanate groups in the modified polyolefin can be identified by IR measurement. Specifically, a press piece of 40 mm x 30 mm x 0.5 mm was prepared using pellets of modified polyolefin, and IR measurement was performed to determine the peak height of the isocyanate group observed around 2243 cm ^-1 . Calculate the absorbance. The peak height of the isocyanate group is 2243 cm ⁻¹ when a straight line connecting 2210 cm ⁻¹ and 2310 cm ⁻¹ is used as the baseline.

<Composition>
A composition may be prepared by blending other components (resin, filler, additives, etc.) with the modified polyolefin.
Other components may be blended before modification of the double bond-containing polyolefin, may be blended during modification, or may be blended after modification.
The amount of other components blended is usually 0.001 to 200 parts by weight per 100 parts by weight of the modified polyolefin.

Examples of fillers include inorganic fillers (talc, calcium carbonate, calcined kaolin, etc.) and organic fillers (fibers, wood flour, cellulose powder, etc.).
Additives include antioxidants (phenol-based, sulfur-based, phosphorus-based, lactone-based, vitamin-based, etc.), weathering stabilizers, ultraviolet absorbers (benzotriazole-based, tridiamine-based, anilide-based, benzophenone-based, etc.), heat Stabilizers, light stabilizers (hindered amine type, benzoate type, etc.), antistatic agents, nucleating agents, pigments, adsorbents (metal oxides such as zinc oxide, magnesium oxide, etc.), metal chlorides (iron chloride, calcium chloride, etc.) ), hydrotalcite, aluminate, lubricant, mineral oil, silicone compound, etc.

<Applications of modified polyolefin>
The modified polyolefin has at least one isoxazoline skeleton and at least one isocyanate group. Since the polyolefin modified product has at least one isocyanate group, it is useful as a reactant with a compound having active hydrogen such as an amine group or a hydroxyl group. Modified polyolefins can be suitably used as crosslinking agents and modifiers in metal, woodworking, automobile refinishing paints, and the like.

EXAMPLES Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.

<Measurement of physical properties, analysis, etc.>
(DSC measurement)
The melting point (Tm) of the double bond-containing polyolefin was determined by differential scanning calorimetry (DSC) measurement. After raising the temperature of the sample to 200°C and leaving it for 5 minutes, the temperature was lowered to 40°C at a cooling rate of 10°C/min, and the endothermic peak was measured again at a heating rate of 10°C/min. The temperature at the top was taken as the melting point. The unit is °C.

(Calculation method of carbon-carbon double bond terminal ratio)
The carbon-carbon double bond terminal ratio of the double bond-containing polyolefin was calculated in accordance with JP-A-2021-4376.
200 mg of the sample was placed in an NMR sample tube with an inner diameter of 10 mm along with 2.4 ml of an o-dichlorobenzene/deuterated bromide benzene (C ₆ D ₅ Br) mixed solution and hexamethyldisiloxane, which is a reference material for chemical shift, and heated at 150°C. The mixture was uniformly dissolved using a block heater. NMR measurements were carried out at 120° C. using an AV400 NMR device manufactured by Bruker Biospin Inc. equipped with a 10 mmφ cryoprobe.

¹ H-NMR was used to quantify the number of terminal carbon-carbon double bonds. The measurement conditions for ¹ H-NMR were a sample temperature of 120° C., a pulse angle of 4.5°, a pulse interval of 2 seconds, and a total number of 512 times. For chemical shifts, the proton signal of hexamethyldisiloxane was set at 0.09 ppm, and chemical shifts of signals due to other protons were based on this.
¹³ C-NMR was used to quantify the number of saturated terminals and the number of LCBs. The measurement conditions for ¹³ C-NMR were a sample temperature of 120° C., a pulse angle of 45°, a pulse interval of 18 seconds, and the number of integrations of 3072 times, and the measurement was performed using a broadband decoupling method. For chemical shifts, the ¹³ C signal of hexamethyldisiloxane was set at 1.98 ppm, and the chemical shifts of other ¹³ C signals were based on this.

Based on the above ¹ H-NMR and ¹³ C-NMR measurement results, the total number of carbon-carbon double bond terminals, total number of terminals, and LCB number were calculated according to the method described in the specification, and the carbon-carbon double bond number was calculated from the following formula. The carbon double bond terminal ratio was calculated.
(Carbon-carbon double bond terminal ratio) = (total number of carbon-carbon double bond terminals) / {((total number of terminals) - (number of LCB)) ÷ 2} x 100
Here, the total number of carbon-carbon double bond ends is the total number of carbon-carbon double bond ends per 1000 monomer units calculated by ¹ H-NMR. The total number of terminals is the total number of terminals per 1000 monomer units calculated by ¹ H-NMR and ¹³ C-NMR. The LCB number is the number of methine carbons at the root of a branched chain having 7 or more carbon atoms per 1000 monomer units calculated by ¹³ C-NMR.

(Identification of isoxazoline skeleton)
The isoxazoline skeleton of the modified polyolefin was identified by ¹ H-NMR. Specifically, the modified polyolefin was placed in an NMR sample tube with an inner diameter of 10 mm along with an o-dichlorobenzene/deuterated bromide benzene (C ₆ D ₅ Br) mixed solution and hexamethyldisiloxane, which is a reference substance for chemical shift. The mixture was uniformly dissolved using a block heater at 150°C. NMR measurements were carried out at 120° C. using an AV400 NMR device manufactured by Bruker Biospin Inc. equipped with a 10 mmφ cryoprobe.

(Identification of isocyanate group)
The isocyanate groups in the modified polyolefin were identified by IR measurement. Specifically, a press piece of 40 mm x 30 mm x 0.5 mm was prepared using pellets of modified polyolefin, and IR measurement was performed to determine the peak height of the isocyanate group observed around 2243 cm ^-1 . Absorbance was calculated. The peak height of the isocyanate group is 2243 cm ⁻¹ when a straight line connecting 2210 cm ⁻¹ and 2310 cm −1 is used as the baseline.
When the absorbance was 0.1 or more, it was determined that isocyanate groups were sufficiently introduced into the modified polyolefin product, and when it was 0.3 or more, it was determined that it was particularly excellent.

<Double bond-containing polyolefin>
(PP1: Propylene homopolymer)
Tm=156°C, carbon-carbon double bond termination rate=65.2%
(PP2: Propylene homopolymer)
Tm=155°C, carbon-carbon double bond termination rate=95.8%
(PP3: Propylene homopolymer)
Tm=147°C, carbon-carbon double bond termination rate=100.9%
(PP4: Propylene homopolymer)
Tm=162°C, carbon-carbon double bond terminal rate=18.2%

<Compound represented by general formula [I]>
Compound represented by the following formula [VI] Synthesized according to Example 2A of International Publication No. 2019/107450.

<Isomerization accelerator>
Calcium stearate (manufactured by NOF Corporation, calcium stearate)

<Production of modified polyolefin>
(Examples 1 to 9 and Comparative Example 1)
A twin-screw kneader "KZW15" manufactured by Technovel Co., Ltd. was used to produce the modified polyolefin.
In a plastic bag, 300 g of double bond-containing polyolefin, a compound represented by formula [VI] in an amount of 2 equivalents to the carbon-carbon double bond of the polyolefin, and a predetermined amount of calcium stearate were mixed, and the mixture was mixed. Obtained. Calcium stearate was used in an amount equivalent to the carbon-carbon double bond of the polyolefin shown in Table 1.
The entire amount of the mixture in the plastic bag was poured into a KZW15 feeder preheated to 180° C., and the reaction was started at a screw rotation speed of 400 rpm. After melt-kneading for 10 seconds, the resulting strand was cut from the die outlet and pellets were collected.

In order to remove unreacted isocyanate compounds from the collected pellets, they were purified using an ultrasonic solvent extraction method according to the description in JP-A-2016-173328. Specifically, the collected pellets were formed into a film with a thickness of 0.1 mm or less, cut into approximately 1 cm square pieces using scissors, placed in a flask with a mixed solvent of chloroform/acetone as an extraction solvent, and heated to approximately 60°C. Fixed to the set ultrasonic extractor. In this state, ultrasonic extraction was performed for 75 minutes, and the film was filtered off using filter paper to obtain a modified polyolefin.

Table 1 shows the absorbance results of Examples and Comparative Examples. Furthermore, the ¹ H NMR spectrum of the modified polyolefin of Example 4 is shown in FIG. As shown in FIG. 1, the signal of the hydrogen atom of R ⁴ in general formula [II] is observed in the range of 4.1 to 4.8 ppm, and the signal of the hydrogen atom of R ⁵ and R ⁶ is observed in the range of 2.3 to 3.3 ppm. It was observed in the range of 0 ppm, and based on this, the presence of the isoxazoline skeleton could be confirmed. The presence of an isoxazoline skeleton was similarly confirmed for the modified polyolefins of Examples 1 to 3 and 5 to 9 by ¹ H-NMR spectra.

<Consideration>
As shown in Table 1, by carrying out an addition reaction between a polyolefin having a terminal ratio of carbon-carbon double bonds of 20% or more and a compound represented by the general formula [I], a short process and industrially advantageous method can be obtained. It can be seen that isocyanate groups can be introduced into polyolefins under certain conditions. From the comparison of Examples 1 and 8 and the comparison of Examples 4 and 9, it is found that Examples 1 and 4, which were melt-kneaded in the presence of an isomerization accelerator, have a high absorbance of isocyanate groups, and are difficult to absorb isocyanate groups into polyolefins. It is preferable because the introduction rate is high.

In the modified polyolefin of Comparative Example 1 using a polyolefin with a carbon-carbon double bond terminal ratio of less than 20%, the absorbance of isocyanate groups was low even though it was melt-kneaded in the presence of an isomerization accelerator. It was low, and it was not possible to sufficiently introduce isocyanate groups into the polyolefin.

By the production method of the present invention, a modified polyolefin into which isocyanate groups have been introduced can be produced in a short process and under industrially advantageous conditions. Moreover, by using the obtained modified polyolefin as a crosslinking agent or a modifier, it can be suitably used for metal, wood, automobile refinishing paints, and the like. As described above, the manufacturing method of the present invention has extremely high industrial value.

Claims (7)

A method for producing a modified polyolefin, the method comprising carrying out an addition reaction between a polyolefin having a carbon-carbon double bond terminal ratio of 20% or more and a compound represented by the following general formula [I],
The modified polyolefin has at least one isoxazoline skeleton and at least one isocyanate group,
A manufacturing method comprising, in any order, adding-reacting the double bond of the polyolefin with at least one nitrile oxide group of the compound, and converting at least one of the nitrile oxide groups in the compound into an isocyanate group. .

In the general formula [I],
s is an integer from 2 to 4,
R ¹ and R ² are each independently a hydrocarbon group having 4 to 10 carbon atoms or a halogenated hydrocarbon group having 4 to 10 carbon atoms,
X is each independently a divalent hydrocarbon group, -O-, -S- or -N(R ³ )-,
R ³ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms,
A is an s-valent organic group. A method for producing a modified polyolefin, the method comprising carrying out an addition reaction between a polyolefin having a carbon-carbon double bond terminal ratio of 20% or more and a compound represented by the following general formula [I],
The polyolefin modified product is represented by the following general formula [II],
A manufacturing method comprising, in any order, adding-reacting the double bond of the polyolefin with at least one nitrile oxide group of the compound, and converting at least one of the nitrile oxide groups in the compound into an isocyanate group. .


In the general formulas [I] and [II],
s is an integer from 2 to 4,
n is an integer from 1 to 3,
s>n,
R ¹ and R ² are each independently a hydrocarbon group having 4 to 10 carbon atoms or a halogenated hydrocarbon group having 4 to 10 carbon atoms,
X is each independently a divalent hydrocarbon group, -O-, -S- or -N(R ³ )-,
R ³ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms,
A is an s-valent organic group,
R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
R ⁷ is the main chain of the polyolefin. The step of converting at least one of the nitrile oxide groups in the compound into an isocyanate group is carried out in the presence of an isomerization promoter. A method for producing a modified polyolefin according to claim 1 or 2. The method for producing a modified polyolefin according to claim 1 or 2, wherein the polyolefin and the compound are subjected to an addition reaction under conditions substantially free of a solvent. The step of causing an addition reaction between the double bond of the polyolefin and at least one of the nitrile oxide groups of the compound, and the step of converting at least one of the nitrile oxide groups in the compound into an isocyanate group, are performed on a mixture of the polyolefin and the compound. The method for producing a modified polyolefin according to claim 1 or 2, which is carried out in one operation of melt-kneading at 80 to 300°C. The method for producing a modified polyolefin according to claim 1 or 2, wherein the carbon-carbon double bond of the polyolefin is a vinyl group or a vinylidene group. A polyolefin modified product obtained by the production method according to claim 1 or 2.